Phosphine (PH3) has been widely used as a fumigant in food storage, but increasing PH3 resistance in major pests makes finding alternative fumigants urgent. Methyl benzoate (MBe), a volatile organic compound regarded to be a food-safe natural product, has recently demonstrated significant toxicity against a variety of insect pests. This study is the first evaluation of the fumigation toxicity of three benzoate compounds, MBe, vinyl benzoate, and ethyl benzoate, against PH3-susceptible and PH3-resistant strains of Rhyzopertha dominica and Sitophilus oryzae. All strains were exposed to the compounds at concentrations up to 20 µL/1.5 L air for 24 h. Compared to vinyl benzoate and ethyl benzoate, MBe induced higher mortality rates in all strains at all concentrations. When food was made available, the lethal median concentration for MBe was 10–17-fold higher than when tested without food. Moreover, no significant differences were observed between the responses of the PH3-susceptible and PH3-resistant strains to the compounds. Notably, S. oryzae was more susceptible to MBe. In laboratory settings, MBe successfully controlled PH3-resistant strains of R. dominica and S. oryzae, making it a viable option for PH3-resistance management. Thus, MBe might be suitable for food security programs as an environmentally benign alternative fumigant.